WO2019146065A1 - Matériau pour résistances non linéaires de courant-tension, et résistance non linéaire de courant-tension et son procédé de fabrication - Google Patents

Matériau pour résistances non linéaires de courant-tension, et résistance non linéaire de courant-tension et son procédé de fabrication Download PDF

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WO2019146065A1
WO2019146065A1 PCT/JP2018/002461 JP2018002461W WO2019146065A1 WO 2019146065 A1 WO2019146065 A1 WO 2019146065A1 JP 2018002461 W JP2018002461 W JP 2018002461W WO 2019146065 A1 WO2019146065 A1 WO 2019146065A1
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current
average particle
oxide
voltage non
zinc oxide
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PCT/JP2018/002461
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English (en)
Japanese (ja)
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靖宣 春日
匠 堀口
鈴木　雄太
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株式会社東芝
東芝エネルギーシステムズ株式会社
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Priority to JP2019567487A priority Critical patent/JP6937390B2/ja
Priority to PCT/JP2018/002461 priority patent/WO2019146065A1/fr
Publication of WO2019146065A1 publication Critical patent/WO2019146065A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
    • H01C7/10—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material voltage responsive, i.e. varistors
    • H01C7/105—Varistor cores
    • H01C7/108—Metal oxide
    • H01C7/112—ZnO type

Definitions

  • Embodiments of the present invention relate to current-voltage non-linear resistor materials, current-voltage non-linear resistors, and methods of making the same.
  • an overvoltage protection device such as a lightning arrester or a surge absorber is used.
  • Overvoltage protection devices such as these have a current-voltage non-linear resistor that exhibits insulation characteristics under normal voltage while exhibiting low resistance characteristics when an abnormal voltage is applied. It is valid.
  • This current-voltage non-linear resistor is mainly composed of zinc oxide (ZnO), and at least one metal oxide is added as an additive to obtain voltage non-linear resistance characteristic (hereinafter also referred to as non-linear resistance characteristic).
  • ZnO zinc oxide
  • the mixture to which the substance is added is mixed, granulated, shaped, and sintered, and the ceramic body (sintered body) is provided.
  • an insulating layer of electrically insulating material is used on the side of this sintered body to prevent flashover from the side during surge absorption. It is used after being formed.
  • a current-voltage non-linear resistor mainly composed of zinc oxide is applied to a lightning arrester due to its excellent non-linear resistance characteristic.
  • a plurality of current-voltage non-linear resistors are stacked. It constitutes a lightning arrester. That is, if it is possible to increase the resistance of the current-voltage non-linear resistor applied to this arrester, the number of current-voltage non-linear resistors provided stacked on the arrester can be reduced.
  • the equipment can be miniaturized.
  • the content of subcomponents such as Bi 2 O 3 , Co 2 O 3 , MnO, Sb 2 O 3 and NiO is limited, and ZnO is further added.
  • a current-voltage non-linear resistor in which the crystal phase of Bi 2 O 3 contained in a sintered body which is a main component is limited. This current-voltage non-linear resistor has high resistance and excellent non-linear resistance characteristics.
  • V 1mA which is the voltage when a 1mA commercial frequency current of the current-voltage non-linear resistor used in the conventional high-performance tank arrester is applied, is approximately 200V / mm to 600V / mm. is there.
  • the prior art as described above has not been able to sufficiently satisfy these requirements.
  • the varistor voltage of the current-voltage non-linear resistor in order to increase the varistor voltage of the current-voltage non-linear resistor to 600 V / mm or more, it is necessary to further suppress the grain growth of zinc oxide particles as the main component, and Sb 2 O having the suppression effect It is necessary to further add subcomponents such as 3 and rare earth elements.
  • the resistance can be increased as the addition amount of these subcomponents increases, the amount of spinel particles mainly composed of Zn 7 Sb 2 O 12 which is an insulator also increases, so the current-voltage The current flow may be uneven throughout the non-linear resistor, and the non-linear resistance characteristic may be degraded.
  • the problem to be solved by the present invention is to provide a current-voltage non-linear resistor material, a current-voltage non-linear resistor, and a method of manufacturing the same, which can achieve high resistance and excellent non-linear resistance characteristics and energy tolerance. It is to be.
  • zinc oxide is used as the main component raw material, and at least bismuth oxide, antimony oxide, manganese oxide, cobalt oxide, nickel oxide, rare earth element R, trivalent as a secondary component raw material.
  • a mixture containing the elements, boron and silver is fired.
  • the relative ratio of the average particle size (D50s) of the auxiliary component material in the mixture to the average particle size (D50z) of the zinc oxide is D50s / D50z ⁇ 0.60.
  • the average particle size (D50z) of the zinc oxide is 700 nm or less.
  • the mixture contains 0.005 to 0.04 wt% of the boron in terms of B 2 O 3 and 0.005 to 0.04 wt% of the silver in terms of Ag 2 O.
  • the relative ratio of boron to silver satisfies the relationship 0.125 ⁇ B 2 O 3 / Ag 2 O ⁇ 1.00.
  • Sectional drawing which shows the current-voltage non-linear resistor of embodiment. 5 is a graph showing the relationship between D50s / D50z and nonlinearity coefficient (V 10 kA / V 1 mA ) for sample numbers 1 to 12 in the examples.
  • FIG. 1 is a cross-sectional view showing an example of the current-voltage non-linear resistor 10 of the embodiment.
  • the current-voltage non-linear resistor 10 of the embodiment is formed on a sintered body 20, an insulating layer 30 covering the side surface of the sintered body 20, and upper and lower surfaces of the sintered body 20.
  • An electrode 40 is provided.
  • the sintered body 20 is a mixture containing zinc oxide as a main component material and at least bismuth oxide, antimony oxide, manganese oxide, cobalt oxide, nickel oxide, rare earth element R, trivalent element, boron and silver as auxiliary component raw materials Is fired.
  • the sintered body 20 contains 0.005 to 0.04 wt% of boron in terms of B 2 O 3 , and 0.005 to 0.04 wt% of silver in terms of Ag 2 O, and The relative ratio of boron to silver satisfies the relationship of 0.125 ⁇ B 2 O 3 / Ag 2 O ⁇ 1.00.
  • the material for the current-voltage non-linear resistor 10 of the embodiment is mainly made of zinc oxide, and at least bismuth oxide, antimony oxide, manganese oxide, cobalt oxide, nickel oxide, rare earth element R, 3 as a secondary component material. It consists of a mixture containing valence elements, boron and silver.
  • the relative ratio of the average particle size (D50s) of the auxiliary component material in the mixture to the average particle size (D50z) of the zinc oxide material is D50s / D50z ⁇ 0.60, and the average particle size of the zinc oxide material is It is 700 nm or less.
  • it contains 0.005 to 0.04 wt% of boron in terms of B 2 O 3 , 0.005 to 0.04 wt% of silver in terms of Ag 2 O, and the relative ratio of boron to silver The following condition is satisfied: 0.125 ⁇ B 2 O 3 / Ag 2 O ⁇ 1.00.
  • the mixture contains zinc oxide as the main component material, but the “main component” here is 90 mol% or more of the ratio in the mixture Means to be.
  • the relative ratio of the average particle size (D50s) of the auxiliary component material in the mixture to the average particle size (D50z) of the zinc oxide material is D50s / D50z ⁇ 0.60, and the average particle size of the zinc oxide material (D50z) Below 700 nm.
  • the secondary component material can be uniformly dispersed in the zinc oxide material.
  • the grain growth of zinc oxide particles proceeds uniformly in the firing process for forming a mixture of a zinc oxide raw material and a subcomponent raw material into a sintered body 20, the effect of suppressing the grain growth of zinc oxide particles is obtained.
  • the resistance of the obtained current-voltage non-linear resistor 10 can be increased even if the addition amount of the subcomponent is small. Furthermore, by making D50s / D50z smaller, the fine structure is made uniform, and the sinterability is also improved, so the density of the sintered body 20 is increased and the porosity of the sintered body 20 is reduced. Thus, a current-voltage non-linear resistor 10 having excellent non-linear resistance characteristics and energy tolerance is obtained.
  • the additive can not work effectively, and conversely, the grain growth of zinc oxide particles is hindered and the sinterability is lowered, so that the non-linearity and energy tolerance Is worse. Further, by setting the average particle diameter of the zinc oxide raw material to 700 nm or less, the reaction of the auxiliary component raw material and the zinc oxide raw material efficiently proceeds, so the non-linear resistance characteristic is improved, but when it exceeds 700 nm, the non-linear resistance characteristic Improvement is not observed.
  • the relative ratio D50s / D50z to the average particle diameter D50z of the zinc oxide material of the average particle diameter D50s of the auxiliary component material is 0.60 or less, and the zinc oxide material And the average particle diameter D50z of It is preferable to set D50s / D50z to 0.50 or less from the viewpoint of high resistance, non-linear resistance characteristics and improvement of energy tolerance, and it is preferable to set the average particle size (D50z) of the zinc oxide raw material to 600 nm or less.
  • the lower limit of D50s / D50z is not particularly limited, but D50s / D50z becomes excessively small, that is, when the average particle diameter D50s of the auxiliary component material becomes excessively smaller than the average particle diameter D50z of the zinc oxide material, the auxiliary component material It is preferable that D50s / D50z be 0.35 or more, because it may cause aggregation and difficulty in uniform dispersion. Also, the lower limit of the average particle diameter D50z of the zinc oxide material is not particularly limited, but if the average particle diameter D50z of the zinc oxide material is excessively small, the uniform dispersion of the zinc oxide material and the subcomponent material is inhibited and the sinterability is deteriorated. It is preferable to set the thickness to 350 nm or more because
  • the average particle size (D50t) of all the raw materials including the zinc oxide raw material and the auxiliary component raw material is preferably 750 nm or less.
  • the average particle size (D50t) of all the raw materials is more preferably 650 nm or less.
  • the average particle diameter D50s of the auxiliary component raw material in the mixture which is a powder, the average particle diameter D50z of zinc oxide, and the average particle diameter D50t of all the raw materials use, for example, a particle size distribution measuring apparatus of laser diffraction / scattering type.
  • the particle size distribution can be calculated by measurement (laser diffraction / scattering type particle size distribution measuring method).
  • the laser diffraction / scattering type particle size distribution apparatus for example, "Microtrac MT3000II series" manufactured by Nikkiso Co., Ltd. can be used.
  • the average particle diameter (D50s, D50z, D50t) said by this embodiment is called a median diameter, and the particle size distribution is measured by the above-mentioned measuring method, and the accumulation of the frequency of particle size is 50%.
  • the diameter be the average particle size (D50s, D50z, D50t).
  • auxiliary component materials of the material for the current-voltage non-linear resistor 10 of the embodiment include at least bismuth oxide, antimony oxide, manganese oxide, cobalt oxide, nickel oxide, rare earth element R, boron and silver.
  • boron which is an accessory component of the mixture, in terms of B 2 O 3 , and contains 0.005 to 0.04 wt% of silver in terms of Ag 2 O, and
  • the relative ratio of boron to silver satisfies the relationship of 0.125 ⁇ B 2 O 3 / Ag 2 O ⁇ 1.00.
  • the content of boron in the mixture is preferably 0.006 wt% or more, preferably 0.03 wt% or less, in terms of B 2 O 3 .
  • the content of silver in the mixture is preferably 0.01 wt% or more, and preferably 0.03 wt% or less, in terms of Ag 2 O.
  • the relative ratio of B 2 O 3 and Ag 2 O is preferably in the 0.20 ⁇ B 2 O 3 / Ag 2 O ⁇ 1.00.
  • Bismuth oxide is a component that is present in the grain boundaries of zinc oxide as the main component to develop nonlinear resistance characteristics, but when the content converted to Bi 2 O 3 is smaller than 0.30 mol%, The effect of developing the non-linear resistance characteristic can not be sufficiently obtained, and the energy tolerance may also be deteriorated. If the content is more than 0.80 mol%, the non-linear resistance characteristic may be deteriorated. From these facts, it is preferable that the content of bismuth oxide be 0.30 to 0.80 mol% in terms of Bi 2 O 3 .
  • Antimony oxide forms spinel particles with zinc oxide to suppress grain growth of zinc oxide particles during sintering, and has a function to homogenize, and is a component having an effect to improve non-linear resistance characteristics.
  • the content converted to Sb 2 O 3 is less than 1.50 mol%, the effect of improving the non-linear resistance characteristic can not be sufficiently obtained, and the energy tolerance may also be deteriorated.
  • the content is more than 3.50 mol%, the amount of the insulating component inside the sintered body is increased, and the energy tolerance characteristic may be deteriorated. From these facts, the content of antimony oxide is preferably 1.50 to 3.50 mol% in terms of Sb 2 O 3 .
  • Manganese oxide is an effective component mainly for solid solution in spinel particles to greatly improve non-linear resistance characteristics, but when the content converted to MnO is smaller than 0.50 mol%, this non There is a possibility that the effect of improving the linear resistance characteristic can not be sufficiently obtained. Moreover, when the content is larger than 2.00 mol%, the amount of the insulating component inside the sintered body is increased, and the energy tolerance may be deteriorated. From these facts, it is preferable that the content of manganese oxide be 0.50 to 2.00 mol% in terms of MnO.
  • Cobalt oxide is an effective component mainly for forming a solid solution in spinel particles and greatly improving non-linear resistance characteristics, but when the content converted to Co 2 O 3 is smaller than 0.30 mol% There is a possibility that the effect of improving this non-linear resistance characteristic can not be obtained sufficiently.
  • the content is more than 1.50 mol%, the amount of the insulating component inside the sintered body is increased, and the energy tolerance may be deteriorated. From these facts, the content of cobalt oxide is preferably 0.30 to 1.50 mol% in terms of Co 2 O 3 .
  • Nickel oxide is an effective component mainly for forming a solid solution in spinel particles and greatly improving non-linear resistance characteristics, but when the content converted to NiO is smaller than 1.50 mol%, this component is effective. There is a possibility that the effect of improving the non-linear resistance characteristic can not be sufficiently obtained. When the content is more than 3.50 mol%, the amount of the insulating component inside the sintered body is increased, and the energy tolerance may be deteriorated. From these facts, the content of nickel oxide is preferably 1.50 to 3.50 mol% in terms of NiO.
  • the mixture also contains a rare earth element as a minor component.
  • a rare earth element selected from yttrium (Y), europium (Eu), eribium (Er), thulium (Tm), gadolinium (Gd), dysprosium (Dy), holmium (Ho), ytterbium (Yb)
  • Y yttrium
  • Eu europium
  • Er eribium
  • Tm thulium
  • Gd gadolinium
  • Dy dysprosium
  • Ho holmium
  • Yb ytterbium
  • the mixture also contains a trivalent element as an accessory component.
  • a trivalent element as an accessory component.
  • it contains at least one trivalent element of aluminum (Al), gallium (Ga), and indium (In), and is 0.003 to 0.010 mol% in terms of Al 3+ , Ga 3+ , and In 3+ , respectively. It is preferable to include.
  • the trivalent element is an effective component for solid solution in ZnO particles and greatly improving non-linear resistance characteristics, but when the content is larger than 0.010 mol%, the non-linear resistance characteristics deteriorate There is a risk of
  • the material for the current-voltage non-linear resistor 10 according to the embodiment has been described above, but the current-voltage non-linear resistor 10 according to the embodiment is formed by firing the material for the current-voltage non-linear resistor 10 A sintered body 20 is provided.
  • the 50% breaking strength of the mechanical strength of the sintered body 20 is preferably 140 MPa or more.
  • the mechanical strength of the sintered body can be measured by a four-point bending test in accordance with JIS R1604. When the 50% breaking strength of the mechanical strength of the sintered body is 140 MPa or more, it is possible to obtain an excellent energy resistance which absorbs a lightning impulse surge.
  • the varistor voltage (V 1mA ) which is a voltage when a current of 1 mA commercial frequency is supplied, can be 900 V / mm or more.
  • the method of manufacturing the current-voltage non-linear resistor 10 is based on zinc oxide as the main component material as described above, and at least bismuth oxide, antimony oxide, manganese oxide, cobalt oxide, nickel oxide, rare earth element R, as auxiliary component materials.
  • This is a method including the step of firing a mixture containing a trivalent element, boron and silver (a material for a current-voltage non-linear resistor) to produce a sintered body 20. The details will be described below.
  • the mixture contains zinc oxide which is a main component material, and at least bismuth oxide, antimony oxide, manganese oxide, cobalt oxide, nickel oxide, rare earth element R, boron and silver as auxiliary component materials, and boron is converted to B 2 O 3
  • B 2 O 3 contains 0.005 to 0.04 wt% of silver in terms of Ag 2 O, and the relative ratio of boron to silver is 0.125 ⁇ B 2 O 3 / Ag
  • the mixture is weighed so as to satisfy the relationship of 2 O ⁇ 1.00.
  • Bi 2 O 3 , Sb 2 O 3 , Co 2 O 3 , MnO auxiliary component materials
  • NiO in terms of R 2 O 3, Ag 2 O and B 2 O 3, a Bi 2 O 3 0.30 ⁇ 0.80mol%
  • MnO Containing 0.50 to 2.00 mol% of Co 2 O 3 , 0.30 to 1.50 mol% of Co 2 O 3 , 1.50 to 3.50 mol% of NiO, and 0.10 to 0.50 mol% of R 2 O 3 Is preferred.
  • a trivalent element When a trivalent element is contained, it contains at least one trivalent element of aluminum (Al), gallium (Ga), and indium (In), and when converted to Al 3+ , Ga 3+ , and In 3+ , 0. It is preferable to contain 003 to 0.010 mol%.
  • the prepared mixture and a binder solution adjusted to have a content of 30 to 60% by weight of the mixture are introduced into a wet grinding apparatus, and the average particle size of the zinc oxide raw material becomes 700 nm or less,
  • the slurry is prepared by pulverizing and mixing so that the relative ratio of the average particle diameter (D50s) of the auxiliary component material to the average particle diameter (D50z) of the zinc oxide material is D50s / D50z ⁇ 0.60.
  • a binder solution for example, an aqueous solution obtained by mixing water and an organic binder such as polyvinyl alcohol is used.
  • a wet pulverizing apparatus for example, a circulating apparatus using zirconia beads having a diameter of 0.05 to 0.3 mm is used. Further, the bead packing ratio in the vessel in the wet pulverizing apparatus can be 35 to 95%, the peripheral speed of the stirring rotor can be operated at 500 to 1500 rpm, and the circulating flow rate can be operated at 5 to 50 L / min.
  • the prepared slurry is sprayed and granulated by a rotating disc method or a pressure nozzle method to prepare granules having a cumulative average particle diameter (median diameter D50) of 45 to 90 ⁇ m.
  • the obtained granules are formed into a cylindrical shape by, for example, a hydraulic press forming machine to produce a formed body.
  • the compact is heated to a first temperature of 350 to 500 ° C., and maintained at this temperature, for example, for 1 to 3 hours to remove the binder solution.
  • the molded body is heated to a second temperature, that is, a temperature of 900 to 1300 ° C., and maintained at this temperature, for example, for 2 hours or more, and fired.
  • a second temperature that is, a temperature of 900 to 1300 ° C.
  • baking is performed, for example, using a tunnel type continuous furnace and installing a molded object in refractory containers, such as an alumina and a mullite.
  • the heating rate from the first temperature to the second temperature is preferably 25 to 100 ° C./hour from the viewpoint of temperature uniformity in the material to be fired and a firing process lead time.
  • the fired compact is cooled.
  • the cooling method is not particularly limited, but the cooling rate at the time of cooling is preferably 100 to 200 ° C./hour from the viewpoint of temperature uniformity in the material to be fired and the firing process lead time.
  • a sintered body 20 is obtained through this cooling step.
  • an inorganic insulating material such as glass frit, which is an electrical insulating material, is applied or sprayed to the side surface of the cooled cylindrical sintered body 20, and heat treatment is performed at a temperature of 300 to 500 ° C. for 1 to 5 hours.
  • the insulating layer 30 is formed. Further, upper and lower end surfaces of the sintered body 20 are polished, and the conductive material described above is sprayed, for example, on the polished surface to form the electrode 40.
  • the order of performing the process of forming the insulating layer 30 and the process of forming the electrode 40 is not particularly limited, and any process may be performed first.
  • the current-voltage non-linear resistor 10 is manufactured through the above-described steps.
  • the raw material of the sintered body 20 constituting the current-voltage non-linear resistor 10 is oxidized as the main component
  • the average particle size of the zinc material is 700 nm or less, and the relative ratio of the average particle size (D50s) of the subcomponent material to the average particle size (D50z) of the zinc oxide material is D50s / D50z ⁇ 0.6.
  • the sintered body 20 can be densified, and the zinc oxide particles in the sintered body 20 can be miniaturized.
  • the varistor voltage (V 1 mA ) of the current-voltage non-linear resistor 10 having the sintered body 20 can be increased to 900 V / mm or more.
  • boron which is a secondary component material, in terms of B 2 O 3 , and contains 0.005 to 0.04 wt% of silver in terms of Ag 2 O, and
  • Example 1 In Example 1, the average particle diameter (D50z) of the zinc oxide raw material and the average particle diameter (D50s) of the subcomponents in the mixture at the time of producing the sintered body are relative to the average particle diameter (D50z) of the zinc oxide raw material The influence of the ratio D50s / D50z on the varistor voltage (V 1 mA ), non-linear resistance characteristic and energy tolerance characteristic of the current-voltage non-linear resistor will be described.
  • zinc oxide (ZnO) was used as a main component of a raw material of a sintered body.
  • the subcomponent materials 0.50 mol% of bismuth oxide (Bi 2 O 3), three antimony oxide (Sb 2 O 3) and 2.00 mol%, manganese oxide (MnO) 0.50mol%, cobalt oxide (Co 1.00 mol% of 2 O 3 ), 2.00 mol% of nickel oxide (NiO), 0.30 mol% of yttrium oxide (Y 2 O 3 ) as a rare earth element, 0.02 wt% of boron (B 2 O 3 ) Prepared by adding 0.02 wt% of silver (Ag 2 O) and aluminum as a trivalent element to an aqueous solution of aluminum hydroxide (Al 2 O 3 ) and adding 0.005 mol%, zinc oxide raw material and these subcomponents A mixture of raw materials was prepared. The balance is zinc oxide.
  • the uniformly mixed slurry was obtained by the grinding and mixing process in this wet grinding apparatus.
  • the average particle size (D50z) of zinc oxide and the average particle size (D50s) of all the subcomponents are the particle size distribution measuring apparatus of a laser diffraction / scattering type (a slurry manufactured by Nikkiso Co., Ltd.) It measured using "Microtrac MT3000II series".
  • this average particle diameter is an average particle diameter in median diameter.
  • this slurry was spray granulated with a spray drier so that the cumulative average particle size would be 45 to 90 ⁇ m.
  • the obtained granulated powder was made into a cylindrical compact having a diameter of 125 mm and a thickness of 30 mm by a hydraulic press-forming machine.
  • this molded body was heated to a first temperature of 500 ° C., and maintained at this temperature for 2 hours to remove an organic binder and the like.
  • the molded body was heated to a second temperature of 1050 ° C., and maintained at this temperature for 3 hours for firing.
  • baking was performed by installing a compact in a mullite refractory container using a tunnel type continuous furnace.
  • the heating rate from the first temperature of 500 ° C. to the second temperature of 1050 ° C. was 100 ° C./hour.
  • the fired compact was cooled to 750 ° C. or less.
  • the cooling rate at the time of cooling to the temperature of 750 degrees C or less was 100 degrees C / hr. A sintered body was obtained through this cooling step.
  • a glass frit was applied to the side surface of the sintered body as a cooled compact, and heat treatment was performed at a temperature of 500 ° C. for 2 hours to form an insulating layer. Furthermore, the upper and lower end surfaces of the sintered body were polished, and aluminum was sprayed on this polished surface to form an electrode, whereby a current-voltage non-linear resistor was obtained.
  • V 1 mA The varistor voltage (V 1 mA ), the non-linear resistance characteristic and the energy resistance were evaluated for the current-voltage non-linear resistors of the obtained sample Nos. 1 to 12.
  • V 1 mA The varistor voltage (V 1 mA ), which is the voltage when a current of 1 mA commercial frequency was applied, was measured according to JEC 0202-1994. It was confirmed that the value of this varistor voltage (V 1 mA ) was 900 V / mm or more.
  • Table 1 shows the average particle sizes (D50t) of all the raw materials including the zinc oxide raw material and the auxiliary component raw materials, the average particle sizes of zinc oxide (D50z), and D50s in the current-voltage non-linear resistors of sample numbers 1 to 12.
  • / D50z varistor voltage (V 1 mA ), non-linearity coefficient (V 10 kA / V 1 mA ) and energy tolerance are shown.
  • * mark is a comparative example which shows the sample which is out of the range of this embodiment.
  • FIG. 2 is a diagram showing the relationship between D50s / D50z and the non-linearity coefficient (V 10kA / V 1mA ) for sample numbers 1 to 12.
  • the varistor voltage (V 1mA ) is 900 V / mm or more
  • the non-linearity coefficient (V 10kA / V 1mA ) is 1 It has been found that the energy tolerance is less than 300 and the energy tolerance is greater than 400 J / cc.
  • the current-voltage non-linear resistor according to the present embodiment can achieve higher resistance and has excellent non-linear resistance characteristics and energy tolerance as compared with the comparative example.
  • the relative ratio of the average particle diameter (D50s) of the auxiliary component material to the average particle diameter (D50z) of the zinc oxide material is D50s / D50z ⁇ 0.60, and the average particle diameter of the zinc oxide material is 700 nm or less, containing 0.005 to 0.04 wt% of boron in terms of B 2 O 3 , containing 0.005 to 0.04 wt% of silver in terms of Ag 2 O, and the relative amount of boron to silver
  • the current-voltage non-linear resistor having a sintered body obtained by firing a mixture satisfying the relationship of a ratio of 0.125 ⁇ B 2 O 3 / Ag 2 O ⁇ 1.00 high resistance can be achieved. It has been found that excellent non-linear resistance characteristics and energy tolerance are obtained.
  • Example 2 In Example 2, the effect of the component content of boron and silver on the energy tolerance of the current-voltage non-linear resistor in the mixture at the time of producing the sintered body will be described.
  • the grinding and mixing treatment in a wet grinding apparatus is performed so that the average particle size (D50t) of all the raw materials is 695 nm, the average particle size (D50z) of zinc oxide is 700 nm, and D50s / D50z is 0.50 for all samples. Control the conditions.
  • the average particle size (D50t) of all the raw materials, the average particle size (D50z) of zinc oxide, and the average particle size (D50s) of all the subcomponents were measured in the same manner as in Example 1.
  • the varistor voltage (V 1 mA ), the non-linear resistance characteristic and the energy resistance were evaluated for the current-voltage non-linear resistors of the obtained sample numbers 13 to 24.
  • the experimental conditions and method in the evaluation of the varistor voltage (V 1 mA ), the non-linear resistance characteristic and the energy tolerance, and the evaluation criteria were the same as the experimental conditions and the experimental method of Example 1 described above.
  • 10 pieces of each of the current-voltage non-linear resistors of sample numbers 13 to 24 were prepared, and the 10 pieces were tested and their averages were evaluated.
  • Table 2 shows the composition components of boron and silver, varistor voltage (V 1 mA ), non-linearity coefficient (current-voltage non-linear resistors) of sample No. 4 (see table 1) and sample Nos. 13 to 24. V 10 kA / V 1 mA ) and energy tolerance are shown.
  • * mark is a comparative example which shows the sample which is out of the range of this embodiment.
  • the varistor voltage (V 1mA ) is 900 V / mm or more and the non-linearity coefficient (V 10kA / V 1mA ) is 1 It has been found that the energy tolerance is less than 300 and the energy tolerance is greater than 400 J / cc. In addition, it was found that the current-voltage non-linear resistor according to the present embodiment can achieve higher resistance and has excellent non-linear resistance characteristics and energy tolerance as compared with the comparative example.
  • the relative ratio of the average particle diameter (D50s) of the auxiliary component material to the average particle diameter (D50z) of the zinc oxide material is D50s / D50z ⁇ 0.60, and the average particle diameter of the zinc oxide material is 700 nm or less, contains 0.005 to 0.04 wt% of boron as B 2 O 3 as a subcomponent material, and 0.005 to 0.04 wt% of silver as Ag 2 O
  • a current-voltage non-linear resistor comprising a sintered body obtained by firing a mixture satisfying the relation of 0.125 ⁇ B 2 O 3 / Ag 2 O ⁇ 1.00 in the relative ratio of boron to silver It has been found that high resistance can be achieved, and excellent non-linear resistance characteristics and energy tolerance can be obtained.
  • Example 3 zinc oxide (ZnO) is a main component in the mixture at the time of producing the sintered body, and bismuth (Bi), antimony (Sb), manganese (Mn), cobalt (Co), nickel as a secondary component. The influence of each content of (Ni) on the characteristics of the current-voltage non-linear resistor will be described.
  • the grinding and mixing treatment in a wet grinding apparatus is performed so that the average particle size (D50t) of all the raw materials is 695 nm, the average particle size (D50z) of zinc oxide is 700 nm, and D50s / D50z is 0.50 for all samples. Control the conditions.
  • the average particle size (D50t) of all the raw materials, the average particle size (D50z) of zinc oxide, and the average particle size (D50s) of all the subcomponents were measured in the same manner as in Example 1.
  • the varistor voltage (V 1 mA ), the non-linear resistance characteristic and the energy resistance were evaluated for the obtained current-voltage non-linear resistors of sample numbers 25 to 48.
  • the experimental conditions and method in the evaluation of the varistor voltage (V 1 mA ), the non-linear resistance characteristic and the energy tolerance, and the evaluation criteria were the same as the experimental conditions and the experimental method of Example 1 described above.
  • 10 pieces of each of the current-voltage non-linear resistors of sample numbers 25 to 48 were prepared, and the 10 pieces were tested and the average was evaluated.
  • composition components (raw material addition amount) of subcomponents of the mixture in the current-voltage non-linear resistors of sample No. 4 (see Table 1) and sample Nos. 25 to 48, varistor voltage (V 1 mA ), non-linearity factor (V 10 kA / V 1 mA ) and energy tolerance.
  • V 1 mA varistor voltage
  • V 10 kA / V 1 mA energy tolerance
  • * mark is a comparative example which shows the sample which is out of the range of this embodiment.
  • the varistor voltage (V 1mA ) is 900 V / mm or more and the non-linearity coefficient (V 10kA / V 1mA ) is 1 It has been found that the energy tolerance is less than 300 and the energy tolerance is greater than 400 J / cc. In addition, it was found that the current-voltage non-linear resistor according to the present embodiment can achieve higher resistance and has excellent non-linear resistance characteristics and energy tolerance as compared with the comparative example.
  • each Bi 2 O 3, Sb 2 O 3, Co 2 O 3, MnO in terms of NiO, Bi 2 O 3 and 0.30 to 0.80 mol%, 1.50 to 3.50 mol% of Sb 2 O 3 , 0.50 to 2.00 mol% of MnO, 0.30 to 1.50 mol% of Co 2 O 3 , 1.50 to NiO 3.50 mol%, containing 0.005 to 0.04 wt% of boron converted to B 2 O 3 , containing 0.005 to 0.04 wt% of silver converted to Ag 2 O, and boron silver
  • the relative ratio to the above satisfies the relationship of 0.125 ⁇ B 2 O 3 / Ag 2 O ⁇ 1.00, and the relative ratio of the average particle diameter (D50s) of the auxiliary component material to the average particle diameter (D50z) of the zinc oxide material Is D50s / D50z ⁇ 0.60, In the current-voltage non-linear resist
  • Example 4 In Example 4, the influence of the addition of the rare earth element on the characteristics of the current-voltage non-linear resistor in the mixture at the time of producing the sintered body will be described.
  • the grinding and mixing treatment in a wet grinding apparatus is performed so that the average particle size (D50t) of all the raw materials is 695 nm, the average particle size (D50z) of zinc oxide is 700 nm, and D50s / D50z is 0.50 for all samples. Control the conditions.
  • the average particle size (D50t) of all the raw materials, the average particle size (D50z) of zinc oxide, and the average particle size (D50s) of all the subcomponents were measured in the same manner as in Example 1.
  • the varistor voltage (V 1 mA ), the non-linear resistance characteristic and the energy resistance were evaluated for the obtained current-voltage non-linear resistors of sample numbers 49 to 80.
  • the experimental conditions and method in the evaluation of the varistor voltage (V 1 mA ), the non-linear resistance characteristic and the energy tolerance, and the evaluation criteria were the same as the experimental conditions and the experimental method of Example 1 described above.
  • 10 pieces of each of the current-voltage non-linear resistors of sample numbers 49 to 80 were prepared, and the 10 pieces were tested and the average was evaluated.
  • Table 4 shows the composition of the rare earth element, the varistor voltage (V 1 mA ), and the non-linearity coefficient (V) in the current-voltage non-linear resistors of sample No. 4 (see Table 1) and sample Nos. 49 to 80. 10 kA / V 1 mA ) and energy tolerance.
  • * mark is a comparative example which shows the sample which is out of the range of this embodiment.
  • the varistor voltage (V 1mA ) is 900 V / mm or more and the non-linearity coefficient (V 10kA / V 1mA ) is It was found that the energy tolerance is smaller than 1.300 and larger than 400 J / cc. In addition, it was found that the current-voltage non-linear resistor according to the present embodiment can achieve higher resistance and has excellent non-linear resistance characteristics and energy tolerance as compared with the comparative example.
  • the relative ratio of the average particle diameter (D50s) of the auxiliary component material to the average particle diameter (D50z) of the zinc oxide material is D50s / D50z ⁇ 0.60, and the average particle diameter of the zinc oxide material is 700 nm or less, contains 0.005 to 0.04 wt% of boron as B 2 O 3 as a subcomponent material, and 0.005 to 0.04 wt% of silver as Ag 2 O
  • the relative ratio of boron to silver satisfies the relation of 0.125 ⁇ B 2 O 3 / Ag 2 O ⁇ 1.00, and further, yttrium (Y), europium (Eu), and eribium (Er) as subcomponent materials.
  • Example 5 describes the influence of the addition of a trivalent element on the characteristics of the current-voltage non-linear resistor in the mixture at the time of producing a sintered pair.
  • the grinding and mixing treatment in a wet grinding apparatus is performed so that the average particle size (D50t) of all the raw materials is 695 nm, the average particle size (D50z) of zinc oxide is 700 nm, and D50s / D50z is 0.50 for all samples. Control the conditions.
  • the average particle size (D50t) of all the raw materials, the average particle size (D50z) of zinc oxide, and the average particle size (D50s) of all subcomponents were measured in the same manner as in Example 1.
  • the varistor voltage (V 1 mA ) and the non-linear resistance characteristics of the obtained current-voltage non-linear resistors of sample numbers 81 to 94 were evaluated.
  • the experimental conditions, the experimental method, and the evaluation criteria in the evaluation of the varistor voltage (V 1 mA ) and the non-linearity were the same as the experimental conditions and the experimental method of Example 1 described above.
  • 10 pieces of each of the current-voltage non-linear resistors of sample numbers 81 to 94 were prepared, 10 pieces were tested, and the average was evaluated.
  • Table 5 shows the compositional components of trivalent elements, varistor voltage (V 1 mA ) and non-linearity coefficient in current-voltage non-linear resistors of sample No. 4 (see Table 1) and sample Nos. 81 to 94. V 10 kA / V 1 mA ) is shown.
  • * mark is a comparative example which shows the sample which is out of the range of this embodiment.
  • the varistor voltage (V 1mA ) is 900 V / mm or more and the non-linearity coefficient (V 10kA / V 1mA ) is 1 It was found to be smaller than .300.
  • the current-voltage non-linear resistor according to the present embodiment had high resistance as a comparative example and had excellent non-linear resistance characteristics.
  • the relative ratio of the average particle diameter (D50s) of the auxiliary component material to the average particle diameter (D50z) of the zinc oxide material is D50s / D50z ⁇ 0.60, and the average particle diameter of the zinc oxide material is 700 nm or less, contains 0.005 to 0.04 wt% of boron as B 2 O 3 as a subcomponent material, and 0.005 to 0.04 wt% of silver as Ag 2 O
  • the relative ratio of boron to silver satisfies the relationship of 0.125 ⁇ B 2 O 3 / Ag 2 O ⁇ 1.00, and further, aluminum (Al), gallium (Ga), indium (In) as a subcomponent material
  • FIG. 1 The subsequent steps of producing a sintered body are the same steps as in Example 1 described above, but there is a difference only in the step of forming the obtained granulated powder by a hydraulic press-forming machine, and the diameter is A sintered body was produced as a cylindrical compact having a thickness of 40 mm and a thickness of 40 mm.
  • the six types of sintered bodies produced were designated as sample numbers 95 to 100, respectively, and the mechanical strength of the sintered bodies was measured for them.
  • the mechanical strength of a sintered compact processed the test piece of 3x4x38 mm from each sintered compact, and measured the bending strength by the 4 point
  • Table 6 shows the 50% breaking strength (MPa) and the breaking average energy ( ⁇ : J / cc) in the energy resistance test for the sintered bodies of sample numbers 95 to 100.
  • * mark is a comparative example which shows the sample which is out of the range of this embodiment.
  • the energy resistance can be improved by setting the 50% breaking strength of the mechanical strength of the sintered body to 140 MPa or more. That is, it was found that by mounting a sintered body having a 50% breaking strength as a component of the current-voltage non-linear resistor, it is possible to further increase the current-voltage non-linear resistor energy resistance. .

Abstract

L'invention concerne un procédé de fabrication d'une résistance non linéaire de courant-tension qui est un procédé dans lequel un mélange contenant de l'oxyde de zinc en tant que matière première de composant principal et contenant également au moins de l'oxyde de bismuth, de l'oxyde d'antimoine, de l'oxyde de manganèse, de l'oxyde de cobalt, de l'oxyde de nickel, un élément de terre rare R, du bore et de l'argent en tant que matières premières de composant auxiliaire. Le rapport relatif du diamètre de particule moyen (D50s) des matières premières de composant auxiliaire au diamètre de particule moyen (D50z) d'oxyde de zinc dans le mélange est inférieur ou égal à 0,60 (D50s/D50z ≤ 0,60). le diamètre particulaire moyen (D50z) de l'oxyde de zinc est inférieur ou égal à 700 nm. Le mélange contient du bore en une quantité de 0,005 à 0,04% en poids en termes de teneur en B2O3, et contient de l'argent en une quantité de 0,005 à 0,04% en poids en termes de teneur en Ag2O. Le rapport relatif de la teneur en bore à la teneur en argent satisfait la relation représentée par la formule : 0,125 ≤ B2O3/Ag2O ≤ 1,00.
PCT/JP2018/002461 2018-01-26 2018-01-26 Matériau pour résistances non linéaires de courant-tension, et résistance non linéaire de courant-tension et son procédé de fabrication WO2019146065A1 (fr)

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PCT/JP2018/002461 WO2019146065A1 (fr) 2018-01-26 2018-01-26 Matériau pour résistances non linéaires de courant-tension, et résistance non linéaire de courant-tension et son procédé de fabrication

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04116901A (ja) * 1990-09-07 1992-04-17 Ngk Insulators Ltd 電圧非直線抵抗体とその製造方法
JP2007173313A (ja) * 2005-12-19 2007-07-05 Toshiba Corp 電流−電圧非直線抵抗体
JP2012231091A (ja) * 2011-04-27 2012-11-22 Toshiba Corp 電流−電圧非直線抵抗体

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04116901A (ja) * 1990-09-07 1992-04-17 Ngk Insulators Ltd 電圧非直線抵抗体とその製造方法
JP2007173313A (ja) * 2005-12-19 2007-07-05 Toshiba Corp 電流−電圧非直線抵抗体
JP2012231091A (ja) * 2011-04-27 2012-11-22 Toshiba Corp 電流−電圧非直線抵抗体

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